JPS61162554A - Colored resin composition - Google Patents

Abstract

PURPOSE:To produce the titled composition containing a colorant in a uniformly dispersed state, and having improved properties such as resistance to bleeding- out of the colorant, by compounding a colorant-containing thermoplastic polymer as a separated phase. CONSTITUTION:A thermoplastic polymer (e.g. styrene polymer) filled with a colorant (e.g. organic dye, organic pigment, etc.) is dispersed uniformly in a matrix composed of a thermoplastic polymer (e.g. a solvent-soluble polyester preferably having a crystallinity of <5%, a softening point of 40-150 deg.C and a number-average molecular weight of 500-30,000) under melting and kneading. The average diameter of the separated phase is <=10mu, preferably <=5mu, and the electrical attractive force between the polymer of the separated phase and the colorant is made to be larger than the attractive force between the polymer in the matrix phase and the colorant.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is characterized by containing a colorant in a specific form.
The present invention relates to a resin composition that is uniformly colored and prevents deterioration of various properties caused by filling with a colorant.

More specifically, the present invention relates to a colored resin composition suitable for the field of colored materials, which is uniformly and finely dispersed even when a coloring agent is blended therein, and prevents deterioration of various properties caused by colorants such as bleed-out. .

Thermoplastic polymers are widely used in various fields due to their mechanical properties and excellent moldability.

Due to the wide range of applications, there are many fields that require coloring, and coloring is expected to lead to even more applications.

It is desirable that the coloring operation be as simple as possible, such as by simple mixing. However, when a colorant is blended with a thermoplastic polymer, uneven dispersion may cause unevenness, or in severe cases, bleeding may occur on the surface, or the presence of the colorant may cause the inherent properties of the thermoplastic polymer to change.
For example, surface properties such as charging properties, paintability, and chemical resistance may be significantly impaired, making it impossible to obtain a product that can be read and used for practical purposes.

The purpose of the present invention is to solve all at once the problems encountered when coloring such thermoplastic polymers, namely uneven dispersion such as mottled patterns and deterioration of surface properties. .

The present invention addresses this problem by distributing the functions of the colorant and the thermoplastic polymer into a matrix (continuous phase) and a dispersed phase in the composition in order to clearly distinguish between them. That is, the above objective is achieved by sealing the coloring agent in the dispersed phase to prevent it from coloring the thermoplastic polymer of the matrix, and further dispersing the dispersed phase finely and uniformly to measure the uniformity of coloring. This was done after discovering that.

Therefore, the colored resin composition according to the present invention has a thermoplastic polymer matrix and a thermoplastic polymer dispersed phase that is dispersed in the matrix and is phase-separated from the matrix phase. It is characterized in that substantially all of the coloring agent is filled in the polymer.

挌-1 According to the present invention, the above-mentioned objects have been achieved, and the composition of the present invention has a colorant uniformly dispersed therein, and there is no deterioration of surface properties due to bleed-out of the colorant.

Matrix The types of thermoplastic polymers that should constitute the matrix in the present invention include: 1) ethylene, propylene, butene-1,
Pentene-1,4-methylpentene-1, hexene-1
In addition to copolymers of α-olefins (including ethylene) alone or with each other, block, random or graft copolymers of a majority weight of these α-olefins with other unsaturated compounds, or single copolymers of these α-olefins (including ethylene). Or so-called olefin polymers such as modified copolymers treated with halogenation, sulfonation, oxidation, etc., acrylonitrile-
Examples include resins and rubbers such as styrene copolymer (As resin), polycarbonate, thermoplastic polyester, polyamide, polystyrene, styrene-butadiene-styrene block copolymer, polyacrylonitrile, and methyl methacrylate resin.

Regarding the above-mentioned olefin polymer, other unsaturated compounds that can be copolymerized with α-olefin include vinyl esters such as vinyl acetate, vinyl silanes such as vinyltrimethoxysilane and nyltriacetoxysilane, and the above-mentioned examples. Examples include ethylenically unsaturated monomers other than the α-olefin of the polymer.

Among the thermoplastic polymers used in the present invention, those having transparency exhibit the remarkable effects of the present invention. Among these, polyester is one of the preferred matrix phases.

The polyester used in the present invention is appropriately selected from commonly used polyesters obtained by polycondensation of polybasic acids and polyhydric alcohols.

Examples of polybasic acids include aromatic carboxylic acids such as terephthalic acid, isophthalic acid, and trimellidic acid, adipic acid, hexahydroterephthalic acid, succinic acid, n-dodecenylsuccinic acid, iso-dodecenylsuccinic acid, and n-dodecylsuccinic acid. acids, aliphatic carboxylic acids such as n-octylsuccinic acid, iso-octylsuccinic acid, n-butylsuccinic acid, unsaturated carboxylic acids such as maleic acid, fumar H, and anhydrides thereof. In addition, as an alcohol component,
Ethylene glycol, propylene glycol, 1,4-
Butanediol, hexamethylene glycol, neopentyl glycol, 2.2.4°4-tetramethylene glycol, glycerin, trimethylolpropane, bisphenol A1 hydrogenated bisphenol A, sorbitol or their etherified hydroxyl compounds, e.g. polyoxyethylene (10) Sorbitol, polyoxypropylene (5) Glycerin, polyoxyethylene (4)
Pentaerythritol, polyoxypropylene (2,2
)-2,2-bis(4-hydroxyphenyl)propane, polyoxyethylene(2)=2,2-bis(4-hydroxyphenyl)propane, and the like.

Polyesters that exhibit remarkable effects of the present invention are those that are soluble in solvents. those with poor quality or low crystallinity;
In particular, those with a crystallinity of less than 5% as determined by X-ray analysis are particularly effective. The softening point is 40-150℃, especially 60℃.
~130℃, and the number average molecular weight is 50℃.
0 to 30,000, especially 1,000 to 20,000,
Great effect.

On the other hand, a preferred thermoplastic polymer as the polymer constituting the dispersed phase is a styrene polymer. For example, polystyrene or styrene copolymerized with a polymer such as an acrylic ester such as methyl acrylate or a methacrylic ester such as methyl methacrylate or n-butyl methacrylate within a range that does not exceed half-coverage. used. Among them, those having a glass transition temperature of 30 to 105°C and a number average molecular weight of 11,000 to 150,000, particularly 2,000 to 100,000 are particularly effective.

Generally, the matrix polymer and the polymer constituting the dispersed phase are selected to be different types, but they do not necessarily have to be different types of thermoplastic polymers. In other words, even if the polymers are of the same type, their properties such as degree of polymerization, molecular weight, compatibility, etc. may change due to differences in their manufacturing conditions or due to the treatment of one of the polymers, resulting in a state in which they are not uniformly miscible with each other. By doing so, it is possible to form the composition of the present invention.

The dispersed phase consists of such a polymer filled with a colorant (details will be described later).

Dispersed Phase/Colorant The colorant that can be used in the present invention must meet at least the following two requirements.

i) It has the property of penetrating into the thermoplastic polymer constituting the dispersed phase. Therefore, colorants that have a greater affinity for the thermoplastic polymers that make up the dispersed phase than for the thermoplastic polymers that make up the matrix are generally preferred. If the coloring agent does not have the above-mentioned properties as it is, the above-mentioned properties may be imparted by treating it with other components.

In other words, the colorant, either as such or by being treated with other components, is a polymer of at least one component of the thermoplastic polymer that constitutes the dispersed phase rather than the thermoplastic polymer that constitutes the matrix. have a greater affinity for

ii) The size (average dispersion diameter) of the colorant is smaller than the size of the dispersed phase.

The colorant used in the present invention can be used without any problem as long as it does not cause discoloration or abnormality in resin properties during coloring. Specific examples include basic dyes such as rhodamine B, acidic dyes, fluorescent dyes, azo dyes, anthraquinone dyes, azine dyes, metal complex compound dyes, red iron oxide, titanium oxide, cadmium yellow, These include cadmium red, basic dye lake, and phthalocyanine pigments. Among these, dyes or organic pigments, especially the former, are preferred in that they do not impair the transparency of the composition.

One feature of the present invention is that the colorant is filled in the components constituting the dispersed phase. That is,
The interaction of the matrix phase, dispersed phase, and colorant is important, with the affinity of the colorant being greater for the dispersed phase than for the matrix phase. For example, the composition of the present invention
It is necessary that the colorant remains in the dispersed phase, not to mention the solid state at room temperature, but even if the colorant is in a light molten state after undergoing thermal history. In other words, it is important to prevent the colorant from diffusing into the matrix phase.

In order for the colorant to remain within the dispersed phase and not diffuse into the matrix phase, the electrical attraction between the matrix phase resin (A) and the colorant (C) is greater than the electric attraction between the dispersed phase resin (B) and the colorant ( It is desirable to select a combination that increases the electrical attraction between C). Among them, the colorant (C) is electrically (
In particular, if the matrix phase resin (A) J5 and the dispersed phase resin (B) are both negative or the former (A) is neutral and (B) is negative, or when the colorant (C) is electrically negative, matrix phase resin<A) and dispersed phase resin (B
) are both positive, or the former (A) is neutral and dominant (B)
When is positive, the effect of the present invention is significant. Generally, positive adhesives are preferred from the viewpoint of transparency.

In order to make the matrix phase resin (A) and the dispersed phase resin (B) different in electrical properties, a functional group for expressing a predetermined electrical property may be introduced into either one or both. It is preferable to introduce functional groups for expressing mutually contradictory electrical properties (it goes without saying that if a resin having such functional groups already exists, it may be selectively used).

Examples of thermoplastic polymers having such functional groups include unsaturated organic acids, which have negative electrical properties,
The alkyl ester or its anhydride (specifically, acrylic acid, methacrylic acid, maleic acid, itaconic acid and its anhydride, etc.) is used as a vinyl ester with an amine or amide group as having positive electrical properties. Or part 4
Classifying salts, etc. (specifically N,N-dimethylaminoethyl methacrylate, N,N-diethylaminoethyl methacrylate, N-ethyl-N-phenylaminoethyl methacrylate, N,N-dimethylaminepropylmethacrylamide, N,N - diethylaminopropyl methacrylamide, N,N-dimethylaminoethylmethacrylamide, N,N-diethylaminoethylmethacrylamide, vinylpyridine, vinylpiperidine, etc.) as a comonomer; (In the present invention, such a polymer is sometimes referred to as a sensitive polymer.)

Production/Citrus 31 In the composition of the present invention, the dispersed phase is preferably finely and uniformly dispersed in the matrix phase. In the case of mechanical blending of the matrix polymer and the polymer (colorant-containing polymer) constituting the dispersed phase, such a homogeneous dispersion system can be created by changing the composition (molecular weight, molecular weight distribution, copolymerization ratio). , randomness, etc.), blending conditions (device, temperature, mixing speed, time, etc.), etc. can be appropriately selected.

One of the preferred embodiments for preparing a homogeneous dispersion in such mechanical blending is the use of dispersion aids.

The dispersion aid used in the present invention is a thermoplastic polymer that is compatible with the matrix phase, preferably the same as the matrix phase, and a thermoplastic polymer that is compatible with the dispersed phase (preferably the same as the matrix phase) when formed into a polymer. vinyl monomer) and subjected to graft reaction conditions.

The method for obtaining the above-mentioned dispersion aid by subjecting a thermoplastic polymer and a vinyl monomer to graft reaction conditions includes (1) dissolving the thermoplastic polymer in a solvent and adding the vinyl monomer thereto; (2) A method in which a thermoplastic polymer is dissolved in a vinyl monomer and reacted. (3) A method in which thermoplastic polymer particles are suspended in water and a vinyl monomer is added thereto. (4) A method of reacting a thermoplastic polymer dissolved in a vinyl upper suspension suspended in water as droplets; (5) A method of reacting after impregnating the polymer particles with heat. Examples include a method of reacting a plastic polymer with a vinyl monomer in a molten state, and (6) a radiation grafting method. Among them, the preferred method is the method (3) or (4) above.

A polymerization initiator is usually used in this reaction. As the polymerization initiator, those used in general radical polymerization can be used, but from the viewpoint of the temperature of the interlocking reaction, it is recommended to select one with a decomposition temperature in the range of 45 to 110°C, especially 50 to 105°C. preferable. The decomposition temperature here means the temperature at which the decomposition rate of the radical generator becomes 50% when 0.1 mole of polymerization initiator is added to 1 liter of benzene and left at a certain temperature for 10 hours. do.

Specific examples of such initiators include, for example, 2.4-
Dichlorobenzoyl peroxide (54°C), t-butyl peroxypivalate (56°C), 0-methylbenzoyl peroxide (57°C), bis-3,5,5-
1-dimethylhexanoyl peroxide (60°C),
Octanoyl peroxide (61℃), lauroyl peroxide (62℃), benzoyl peroxide (
74°C), t-butylbaroxy 2-ethylhexanoate (74°C), 1,1-bis(butylperoxy)-3,3,5-1-limethylcyclohexane (91
℃), cyclohexanone peroxide (97℃), 2
．． 5-dimethyl-2゜butylperoxybenzoate with 5-dibenzoylperoxyhexane (100°C)! −
(104℃>, di-t-butyl-shiba-oxyphthalate (105℃), methyl ethyl ketone peroxide (
organic peroxides such as dicumyl peroxide (117°C), dil-t-butyl peroxide, azobisisobutyronitrile (65°C), azobis(2,4-
azo compounds such as dimethylvaleronitrile (68°C), 2-t-butylazo-2-cyanobroban (79°C),
Examples include water-soluble peroxides such as hydrogen peroxide and potassium persulfate (approximately 70°C). Here, the temperature in parentheses indicates the decomposition temperature. These can also be used in combination. The amount of the polymerization initiator used is in the range of 0.05 to 30% by weight, preferably O71 to 10% by weight, based on the vinyl monomer.

If the dispersion aid used in the present invention is at least 1% by weight in the resin composition, the dispersed phase will be sufficiently fine and uniform.

Preferably, it is used in an amount of 3% by weight or more, but since the dispersion aid itself is a thermoplastic polymer suitable as a forming material, a colorant directly blended with it may exist as a dispersed phase. It is understood that such cases are within the scope of the present invention.

A preferred dispersion aid for the combination of a polyester preferred as a matrix and a styrenic resin preferred as a dispersed phase is a polyester modified with a styrenic monomer, that is, a polyester grafted with a styrenic monomer.

Generally speaking, the particle size of the dispersed phase in the matrix phase is 10μ
(microns) or less, particularly preferably 5μ or less. The particle size here refers to the average particle size (Hartin's diameter) measured by observing a cross section of a sample using an electron microscope.

Another method of obtaining the compositions of the invention is to apply the dispersion aid consisting of the grafted copolymer in situ (in 5
itu) J formation. That is, for example, the monomers providing the matrix resin (e.g., polyester) and the dispersed phase resin, for example,
Styrene) is graft copolymerized. After graft copolymerization, it is common to knead to ensure uniform dispersion of the dispersed phase.

Support-1-1 1! tJL Yu' - (Manufacture of modified polyester (dispersion aid)) Contents 4 kg of water, 80 g of tricalcium phosphate, and 0.12 g of sodium dodecylbenzenesulfonate were added to a 110 liter autoclave to form an aqueous medium;
A solution prepared by dissolving benzoyl peroxide ("Niver BJ" manufactured by NOF Corporation) 87 in a mixed solution of 640 g of styrene and 160 g of n-butyl methacrylate was added to the solution and stirred.

Polyester particles (amorphous, linear saturated polyester, glass transition temperature 51.1°C, molecular weight approximately 3000)
After charging 1200 g of autoclave and purging the inside of the autoclave with nitrogen, the temperature inside the system was raised to 60° C., and this temperature was maintained for 3 hours to impregnate the vinyl monobase containing the polymerization initiator into the polyester resin particles. Next, 11.4 g of t-butyl peroxyvivalate (Verbutyl PVJ, purity 70%, manufactured by NOF Corporation) was added to the 12! turbid system, and the system temperature was further raised to 65°C for 2 hours. The temperature inside the system was then increased to 9.
The temperature was raised to 0°C and maintained for 3 hours to complete polymerization. After cooling, the contents were taken out and washed with acid and water to obtain modified resin particles 2Ky.

1.521 (Manufacture of styrene polymer) 4 kg of water, 8 C1 of tricalcium phosphate, and 0.12 g of dodecylbenzenesulfone soda were added to a 110 liter autoclave to form an aqueous medium, and to this was added ``Barbutyl PVJ 28''. .67 and [Niver BJ
A solution dissolved in a mixture of 1.1y of styrene, 500g of n-butyl methacrylate, and 10(l) of acrylic acid was added to 20g of autoclave and stirred. After replacing the inside of the autoclave with nitrogen, the temperature inside the system was raised to 65°C. The temperature was maintained for 3 hours.Furthermore, the system temperature was raised to 75°C and held for 3 hours, and then the system temperature was raised to 90°C and maintained for 2 hours to complete polymerization. After cooling, the contents were taken out, washed with acid, washed with water, and dried to obtain copolymer resin 2Kl.

When this product was determined by infrared spectroscopy, it was found that the reaction proceeded almost quantitatively with 70% by weight of styrene, 25% by weight of n-butyl methacrylate, and 5% by weight of acrylic acid.

115 units (styrene polymer!FJTi) Reference example-2
In the same manner as above, a styrene polymer 2Ky was obtained by binary copolymerization using 1.5 kg of styrene and 0.5 kg of n-butyl methacrylate.

Reference Example 4 (Manufacture of Styrene Polymer) 2 kg of a copolymer resin, which is a styrene polymer, was obtained in the same manner as in Reference Example 2, except that acrylic acid was replaced with methacrylate.

Example-1 30 parts by weight of the styrene polymer obtained in Reference Example-2 and rC
, 1, and 5 parts by weight of "Pasic Violet 14" were melt-kneaded at 140° C. in a vented twin-screw extruder.

355 parts by weight of this product, 65 parts by weight of the polyester used in Reference Example-1, and 10 parts by weight of the modified polyester obtained in Reference Example-1 as a dispersion aid were heated at 140°C in a vented twin-screw extruder. Colored composition (I) was obtained by melt mixing.

this! A press sheet was made from the one-color composition, a cross section was made, and the dispersed phase was ion-etched and analyzed using a scanning electron microscope. As a result, the dispersed phase was uniformly fine with an average particle size of 3.0μ. It was dispersed. In addition, a coloring composition was sandwiched between a slide glass and a cover glass on a hot press, and the colorant was melted to 1 wA, and the filling state of the colorant was observed using a transmission optical microscope, and the colorant was dispersed. It was found that the phase was packed.

In Example 1, the same procedure was carried out except that the styrene polymer was replaced with 15 parts by weight of the styrene polymer obtained in Reference Example 2 and 15 parts by weight of the styrene polymer obtained in Reference Example 3. A colored composition (n) was obtained by the method.

When this product was evaluated in the same manner as in Example 1, it was found that the colorant was packed into the dispersed phase and the dispersed phase was 2.3μ
The average particle size of the particles is uniformly and finely dispersed. It was noticed.

Example 3 A colored composition (1) was obtained in the same manner as in Example 2 except that copper phthalocyanine was used as the colorant.

When this product was evaluated in the same manner as in Example 1, it was found that the colorant was packed into the dispersed phase and the dispersed phase was 3.3μ
II! C is uniformly and finely dispersed with an average particle size of ! J was made.

A colored composition (rV) was obtained in the same manner as in Example 1 except that the styrene polymer obtained in Reference Example 4 was used instead.

When this product was evaluated in the same manner as in Example 1, it was found that the colorant was packed into the dispersed phase and the dispersed phase was 3.0μ
It was observed that the particles were uniformly and finely dispersed with an average particle size of .

Example-5 A colored composition (V) was obtained in the same manner as in Example-1 except that the dispersion aid was not used.

When this product was evaluated in the same manner as in Example 1, it was found that the dispersed phase had an average particle size of 6.0 μm and was relatively non-uniformly dispersed, but the colorant was packed in the dispersed phase.

A colored composition (Vl) was obtained in the same manner as in Example 1 except that the styrene polymer obtained in Reference Example 3 was used instead of the styrene polymer.

When this product was evaluated in the same way as in Example 1, it was observed that the dispersed phase was finely dispersed with an average particle size of 3.0μ, but the colorant was not only in the dispersed phase but also in the matrix. The phase was also filled.

: UtU-2 ink Contents: 110 liters of non-quality polyester in an autoclave Fragile saturated polyester: Glass transition temperature 63℃
, molecular weight about 20.000>4209, styrene 600g, n-butyl methacrylate 180g and Example-1
50 g of the coloring agent used in step 1 was added and dissolved at 60° C. with stirring. The viscosity of this solution was 190 tons. In addition, as a radical generator [barbutyl PVj5]
5.79 was added and dissolved, and further 7.2 Lj of sodium dodecylbenzenesulfonate and 2.4 kg of water were added and stirred to perform phase inversion from the oil phase to the aqueous suspension phase. after that,
The inside of the autoclave was flushed with nitrogen H9, and the system temperature was raised to 65°C for 4 hours, and then further raised to 75°C and held for 2 hours to complete the engagement. After cooling, the contents were taken out and washed with water to obtain 1250 g of modified colored resin.

When a press sheet was made from this material and evaluated in the same manner as in Example 1, it was found that the colorant was filled in the dispersed phase of the modified polyester, and the dispersed phase was uniformly and finely dispersed with an average particle size of 2.6μ. Was.

Applicant's agent Kiyoshi Inomata Procedural amendment November 1985 and Sunday

Claims (1)

[Scope of Claims] 1. A polymer comprising a thermoplastic polymer matrix and a thermoplastic polymer dispersed phase dispersed in the matrix and phase-separated from the matrix phase; A colored resin composition, characterized in that substantially the entire amount of a coloring agent is filled therein. 2. Matrix phase polymer (A) and dispersed phase polymer (B)
) and colorant (C), the electrical attraction between B and C is A-C
The composition according to claim 1, which has electrical properties greater than the electrical attraction between the compositions. 3. The colorant (C) is electrically positive, the matrix phase polymer (A) is electrically neutral or negative, and the dispersed phase polymer (B) is electrically negative. Claim 2
The composition described in Section. 4. The composition according to any one of claims 1 to 3, wherein the average particle size of the dispersed phase is 10 microns or less. 5. The composition according to claim 4, wherein the average particle size of the dispersed phase is 5 microns or less. 6. According to any one of claims 1 to 5, wherein the matrix phase contains a polymer obtained by graft copolymerizing a monomer of a dispersed phase polymer to a matrix phase polymer. Compositions as described. 7. The composition according to any one of claims 1 to 6, wherein the matrix phase polymer is a solvent-soluble polyester and the dispersed phase polymer is a styrene polymer. 8. Claims 1 to 7, wherein the colorant is an organic dye
The composition according to any one of paragraphs.